Carboximide compounds



United States Patent 3,004,036 CARBOXIMIDE COMPOUNDS Hsing Yun Fan andHarry G. Durham, Modesto, Cahfi,

assignors to Shell Oil Company, a corporation of Delaware N Drawing.Filed Dec. 30, 1957, Ser. No. 705,787 11 Claims. (Cl. 260-326) Thepresent invention is concerned with hydrocarbons wherein one terminalposition is occupied by a polyhalogenopolycycloalkene and the otherterminal position is occupied by a dicarboximide or derivatives thereof.These compounds have been found to possess significant toxicity towardand inhibition of a wide variety of fungi.

The need for elficient and economical fungicidal and fungistaticcompositions has long been manifest. In spite of this fact, however, avast number of the compounds employed as fungicides have generally beenfound lacking in one or more of the basic requirements of a satisfactoryfungicide. In order to be commercially useful, a fungicidal compositionmust be compatible with adjuvants and other active ingredients; it mustbe economical; it should be soluble in common solvents and stable; andmost important, it must not be toxic to the plants to which it isapplied or to animal life. A prohibitive degree of phytotoxicity underthe conditions uti lized for fungus control and toxicity toward warmblooded animals are among the most common shortcomings of presentfungicides.

It is, consequently, the principal object of the present invention toprovide new and novel compounds which are effective as, fungicides yetdo not manifest prohibitive toxicity toward .warm blooded animals suchas man.

Another object of the present invention is to provide new and novelfungicidal compounds which can be economically prepared, distributed andapplied to plants.

Yet another object of the present invention is to pro vide economicaland stable fungicidal compositions containing these compounds.

Still another object of the present invention is to provide a method ofcombating fungi by applying these compositions to plants.

Other objects and advantages will be apparent from the followingdescription read in conjunction with the appended claims.

Generally speaking, the present invention is concerned with organiccompounds wherein one terminal position is occupied by apolyhalogenopolycycloalkene and the other terminal position is occupiedby dicarboximide or derivative thereof. The term dicarboximide asemployed throughout this specification refers to the group Of thepolyhalogenopolycycloalkenes which occupy one terminal position of thecompounds encompassed by the present invention, halogenatedbicyclo(2.2.l)hept-5- ene rings as shown in the following structuralformula are preferred:

Of equal interest in the dimethanonaphthalene ring structure shown inthe following structural formula:

This basic carbon skeleton consists of not more than five linearly fusedfive membered rings.

The halogenated cycloalkene portion of the molecule may be attacheddirectly to the nitrogen atom of the dicarboximide portion of themolecule, or alternatively, the terminal portions of the molecule may beseparated by an alkyl radical of from 1 to 10 carbon atoms, or an arylradical such as benzyl, tolyl, phenyl, naphthalenyl, or anthracenylgroup or an aralkyl group, the alkyl portion of which has 1 to 10 carbonatoms and the aryl portion of which is a benzyl, tolyl, phenyl,naphthalenyl or anthracenyl group. I

In these formulae X represents hydrogen or halogen (preferably chlorine)and X represents hydrogen, halogen (preferably chlorine) or an alkoxy(preferably meth oxy) group. At least one X should be a halogen.

R may be a straight chain, branched chain or cyclic alkylene group offrom 1 to 10 carbon atoms, an arylene group such as a tolylene,phenylene, naphthylene or anthrylene or an aralkylene group made up ofthe alkylene as described above and arylene groups. R is preferably ashort chain alkylene group. y is 0 to 10.

W represents a straight chain aliphatic group of 2 to 5 carbons(preferably 2) either saturated or having one or more double bonds. Wmay be partially or totally h'alo genated, preferably with chlorine. Wmay also represent an. aryl radical such as benzene, toluene,naphthalene and anthracene or their halogenated derivatives. Each of 2carbon atoms of W are bonded respectively to each of the two carboxylgroups of the decarboximide. When W is an aryl ring, each of twoadjacent carbon atoms of the aryl rings are bonded to acarboxyl group ofthe dicarboximide. The compounds of the present invention may thus beconsidered as dicarboximides having substituted therein halogenatedpolycyclic structures such as a polyhalopolycycloalkenyl radical or ahalogenated 1,4,5,8- dimethanonaphthyl radical. 1 Illustrative of thetypes of compounds envisioned by the present invention are: e

N (1,4,5,6,7,7hexachlorobicyclo(2.2.l )hept-5-en-2-yl)-,

maleimide. N(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S-en-Z-ylmethyl)maleirnide. 2chloro-N-(1,4,5,5,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl)maleimide N (5,6,7,8,9,9hexachloro-l,2,3,4,4a,5,8,8a-octahydro- 1,4,5,8-dimethano-naphthalen-2-ylrnethyl)maleimide 2,3 dichloro N-( 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)-

hept-5-en-2-ylmethyl) succinimide N(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl phthalimide N(1,4,5,6,7,7-hexabromobicyclo(2.2.l)hept-5-en-2-yl)- maleimide 2,3difluoro N-10-(1,4,5,6,7,7-hexafluorobicyclo(2.2.1)-

hept-S-en-Z-yldecyl)pimelimide 2,3 'dibromo N-( l,4,5;6-tetrabromo7,7-dimethoxybicyclo (2.2.1 )hept S-en-Z-yImethyD succinirnide N 2 1,4,5,6-tetrabromo-7,7 -diphentoxybicyclo(2.2.l)-

hept-S -en-2-yl:) ethyl) succinimide N (1,4,5,6,7,7hexachlorobicyclo(2.2.1)hept-5-en-2-yltolyl)maleimide 2 fluoro N-(1,4,5,6,7,7-hexabromobicyclo(2.2.1)hept- 5-en-2-ylbenzyl)maleimide N(5,6,7,8,9,9 hexabromo-l,2,3,4a;5,8,8a-octahydro-1,4,5,8-dimethanonaphthalen-Lylphenyl)maleimide N 1,4,5 ,6,7 ,7hexachlorobicyclo(2.2.l)hept-5-en-2-ylanthryDmaleimide N (1,4,5,6,7,7hexachlorobicyclo(2.2.1)l1ept-5-en-2-ylnaphthyDmaleimide Generallyspeaking, the maleimides ofthe present invention may be prepared byreacting the corresponding maleamic acid with acetic anhydride and thephthalirnides of the present invention may be prepared by reacting thecorresponding amine withphthalic anhydride. The maleamic acidsthemselves are obtained'by reacting the appropriatepolyhalogenopolycycloalkene amine with maleic arihydride. Detailedpreparation of these ma'leanu'c acids is to be found in co-peudingapplication SerialNunibcr 705,782. The preparation of the amines isdescribed in copending application Serial Number 705,781.

Examples of specific preparations of compounds encompassed by thepresent invention follow:

:EXAMPLE 1 N- (5,6,7,8,9,9-hexachloro-J ,2,3 ,4,4 [1,5 ,8,8a-ctdhydr0- I,4,5,8-dimethanonaphthalen-Z-ylmethyl maleimide A mixture of 54 .g.ofN-.(5;6,7,8,8 hexaehloro-l,2,3,4, 4a,5,8,8a'octahydro-l,4,5,'8-dimethanonaphthale'n-2 ylrnethyl)maleamic acid, 90ml. of :acetic anhydride and 3 g. of sodium acetate was heated'at 70 for16 hours then 2 hours at 90. The solution was poured into 250 ml. ofwater and stirred until solid formed. The crude solid was recrystallizedfrom benzene to give 15 g. of serni-pure product, M.P. 156-62.Thebenzene filtrate was taken to dryness and extracted with hexane. Thehexane extract was "taken to dryness and the residue triturated withbenzene. The benzene extract was taken to dryness and-the residuetriturated'with methanol to give more solid, '13 g. MzP. ISO-8.Recrystallization of the-two combined-crops gave 21 g. 'M.P. 160-2', ofpure product of 40% yield. Analysis: Calcd. for CnHmClsNOgYCl, 44.6.Found: C1,

EXAMPLE II N- (1 ,4,5,6,7,7-hexachl0r0bicycl0 (2.2.1 hep t-5-en-2-ylmethyl) phthalimide A solution of .37 g. of 1,4;5,6,7,7hexachlorobicyclo- (2.2.1)hept-S ene-Z-methylarnine hydrochloride in 200ml. of water was made :a'lkaline to .phenolphthalein with 20% NaOHsolution and extracted with hexane. The hexanesolution of freeamine wasthen added to asolution of 15 g. of phthalic anhydridein 200 ml. ofbenzene. After 20 minutes reflux .a solid fell out. It was collected togive "45 "g. of N-'(l,4,5;6,7,7 hexacljlorobicyclo(2.2.1)hept-S-en-Z-ylrnethyl)phthalamic acid, M.P. 180 180151 in'92% yie'lcl.Analyses: 'CalcdJfor C gH ClgNO i Cl, 44.6; neut. equiv. 478. Found: Cl,44I5;'neut.-equiv.'4S0.

The ph'thalamic -a'cid was "heated "for 20 -n1inutes at 180.5". Itevolved water and gave a colorless =li'quid which solidified on cooling.The residue was recrystallized from hexane to give 25 g. (60%) of thepure phthalimide, M.P. 131-2", after one further recrystallization frommethanol. Analysis: Calcd. for C H Cl NO Cl, 46.3. Found: CI, 46.0.

EXAMPLE HI N-(I,4,5,6,7,7-hexachlorobicyclo(2.2.1 )hept-S-en-Z- yl)maleimide A total of 30 g. of N-(1,4,S,6,7,7-hexachlorobicyclo-(2.2.1)hept-5-en-2-yl)maleamic acid was added to a well stirred solutionof 40 ml. of acetic anhydride and 1.5 g. of sodium acetate at 905. Themixture was kept at -5 for 1.5 hours after the-end of "the addition thenit was poured into'water. The'soli'd'whichformedwas collected andextracted with .hot hexane leaving 25 g. of crude product, I'M;P.161-4". Recrystallization of this material from hexane gave 11 g. ofpure product, MZP. 166.9. Analysis: Calcd. for C I-1 61 CI, 53.8. Found:Cl, 53.5. Repetition -.of :the aboveexperiment and further workup withthemother rliquor from the-above experiment-gave 21 goo'fssolidrMrP.164-:6 and 10 g. of solid, MP. 16'3.5. The'total-of 42g. of .N-1,'4,'5,6,7,7, -:hexachlorobicyclo(2.21)hept 5 en-2-;yl) nraleimide :isa 75% overall yield.

EXAMPLE IV T o a'well stirred solution of 50 ml. of acetic-anhydride and3g. of sodium acetateat 100 was slowly-added 58 g. of 2chloro-N-(1,4,5,6,7,7-hexachlorohicyclo(212.l) hept-5-en2-ylmethyl)maleamic acid. Th'eresulting'solutionwas kept at 100 for 30minutes then poured into 400 ml. of water and allowed to stand "for 24hours. The water insoluble gum formed was dissolved -in hot hexane butfailed 'to crystallize upon cooling "the solution. The hexane wasremoved and aportion of the 'oil crystallized from cold pentane to give'1 g.-of -product, M.P. 76-8. The mother liquor was concentrated anddistilledto give a colorless liquid, 13:1. -210' '(025 1.0 'mm.).Recrystallizaion or the distillate "from pentane gave 40 g. (75%) ofth'edesired product, 'MzP.

756. Analysis of material, MIP. '76-8". Calcd. 'for C HsCl gNo z Cl,55.9. Found: C], 55:8.

EXAMPLE V N-(1;4,5,6,7,7=hexachl0rdbicyclo(2.2;19hept 5-en-2-ylmethyl)maleimide There was added 46 grams ofN-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl)maleamicacid to 60 grams of acetic anhydride and lggrams of anhydrous sodiumacetate stirred at 80. The mixture was kept at 100 for one hour thenpoured into 300 ml.- of water .and allowed to stand overnight. A totalof 48 grams of crude N-( 1,4,5 ,6,7,7-hexachlorobicyclo( 2.2. 1hept-S-en- 2-ylmethyl)rnaleimide was collected. The crude'was dissolvedin hothexane and the solution was-filtered. Cooling the filtrate gave 13grams of solid, M.P. 107-109 which had M.P. of 108-l10 afterone morerecrystallization from hexane. This in turn was raised to 112- 113.5upon further recrystallization from methanol. Workup of the motherliquors gave 26 ,grams of solid. M.P. 112-113 from methanol. The :yieldwas 60. Further recrystallization of the 112111315 material frommethanol ,gave analytical material, :M.P. 1 1-3-'1 14. Calcd. for C H CI-NO C, 35.2; H, 1. 7; "Cl, 52.0. Found: C, 35.2; H, 1.5; Cl, 52.1.

EXAMPLE VI 2,3-dichl0r0-N-(1,4,5,6,7,7Jzexadhl0robicyclo(2.2.1hept-5-en-2-ylmethyl )succinimide Chlorine was passed into asolution "of45 grams of N (1,4,5,6,7,7 hexachlorobicyclo(2.2.l)hept 5-en-ylandchlorinated under UV. irradiation for 2.5 hours.

The solvent was removed and the residue triturated with hexane to give asolid M.P. 118-122. One recrystallization from heptane gave 45 grams ofproduct (86%), M.P. l22126. Recrystallization from benzene gave 34.5grams of solid M.P. 125-132 C., 6.5 grams of solid, M.P. 122429.Analyses of solid melting at 125-132. Calcd. for C H cl NO C, 29.9; H,1.45; Cl, 59.0. Found: C, 30.4; H, 1.7; CI, 59.0.

The compounds of the present invention possess fungicidal activity to aWide variety of plant pathogens. In the foliage fungicide screen, threevarieties of bean plants and four foliage fungus diseases were employed.Employing these hosts and pathogens the chemicals were To facilitatedeposit, the primary leaves are oriented to a vertical position bypinning them to a small wire staff. Either the upper or lower epidermisof the leaf is exposed to the spray stream, depending on the surface tobe inoculated.

When the mist type spray and the diluent mixture is applied, a dryinginterval of 1-2 hours is sufiicient before inoculation with sporesuspensions using a specially constructed atomizer. Inoculations withbean mildew are made by dusting conidia over treated plants in thegreenhouse.

After 24 hours incubation at 19 C. and 100% humidity, the plants areremoved to the controlled environment greenhouse for symptondevelopment. Disease control and phytotoxicity assessments are madewithin 7 days.

The following table summarizes the results of screenmg:

TABLE 1.FOLIAGE Funorcmn SCREEN Disease Control Min. Effective Cone.Phytotoxieity Max. Safe (P-P- Oonc. (p.p.m.)

P.p. E.p. U.p. 0.1. L. P. BV

N (1,4, 5,6, 7, 7-Hexachlorobieyclo- (2.2.1)hept-5-en-2-yl-methyl)-maleimide 125 500 125 15 1, 000 500 1, 000 2-Ohloro-N-(1,4,5,6,7,7-hexaehlorobicyclo (2.2.1) hept- 5 -en- 2 ylrnethyDmaleimide 125 250-50063425 32 2, 000 500 1, 000 N- (5,6,7,8,9,9-LE[eXach1oro-1, 2,3,

4, 4a,5,8,8a octahydro -1, 4 -exo,

endo 5,8 dimethanonaphthalen-2-ylmethyl -maleimide 125 1, 000 500 32 1,000 1, 000 1, 000 2, 3-Diehloro-N- (1,4,5,6,7, 7-hexaehlorobieyelo(2.2.1)hept 5 en 2-ylmethyl)succinin1ide 125 250 63 32-63 2, 000 1, 0001, 000 N- (1, 4, 5, 6,7,7-Hexach10robicyclophthalimide 1,000 1,000 1,0001,000 l,000 1,000 1,000 N- (1,4, 5,6,7, 7-I-Iexaehlorobieycloide 250500-1, 000 63 32 500 500 500-1, 000

a P. .=phytophth0m phaseolz' (downy mildew of lime. bean); E.p.=Erysiphepolygom (bean powdery mildew); U.p. romyces phaseoli (bean rust);O.l.=Col.letotrieh um.

b L=Lima bean, P=Pint0 bean, BV=Blaek Valentine bean.

screened for general as well as specific control activity and forphytotoxicity. Diseases and hosts are shown below:

BEAN HOSTS PATHOGENS Phaseolus vulgarts var. Pinto Urognyoes phaseohvar. ta)- P. pulgam's var. Black Valenmoo (rust) Erysiphe polygon/i(powdery ildew) Ool l ctotr ichum lindemuthianmim (anthracnose)Phytophthom p h a. s e o H (downy mildew) These four bean pathogens areof economic importance and represent each of the four classes of fungi.P. phaseoli is closely allied with P. infestans, the important potatoand tomato pathogen. Thus, with the above selection, chemicals can beroutinely screened for general or specific disease control activity andfor phytotoxicity on a moderately susceptible plant type.

The test is carried out according to the following procedure: Testchemicals are prepared as 1% w./v. stock solutions in a solvent Thestock is diluted for spraying using a diluent consisting of distilledwater+solvent (1:1 or with distilled water plus two solvents (2:1:1).Triton X-l55, at 0.005% W. is used as a wetting agent for eachconcentration of toxicant. All chemicals are initially tested at asingle concentration of 1000 p.p.m. If acceptable disease control isshown, the chemicals are retested at 1000 ppm. and the next lowestdilution of 500 ppm. Chemicals continuing to show disease control areretested in this fashion until the minimum effective concentration isdetermined. Phytotoxicity assessments are expressed as the maximum Safeconcentration.

Spray applications are made using a laboratory sprayer. The bean plantsare selected for use at a stage when the two primary'leaves are aboutthree-quarters expanded.

tine P. limensis var. Fordhook The effectiveness of the presentcompounds as fungicidm is further evidenced by the following tests:

To obtain expanded disease control data, chemicals were sprayed asemulsions, solutions, or suspensions using concentrations of 0.24% w.,0.12% w. and 0.06% w. These correspond respectively to 2, 1, and 0.5pound of toxicant per gallons of spray. Plants were sprayed to theirrun-off stage, dried for 24 hours, and inoculated with test fungusspores. After inoculation, the plants were held for 24-48 hours in ahumidified incubation chamber at 19 C. They were then removed to thegreenhouse for disease and phytotoxicity development.

Crops and diseases used were tomato or potato blight (Phytophzhorainfestanzs), celery blight (Septoria apiigraveolentis), bean mildew(Erysiphe polygom'), bean rust (Uromyces appendiculatus), and cucumberanthracnose (Colletotrichum lagenarium).

From four replicated plants per concentration, a percentage diseasecontrol figure was obtained, which was based upon the improvement shownover the untreated checks as follow:

disease rating of untreated check -disease rating of treatment orstandard disease rating of untreated check The percent disease controlfor a treatment was next compared with the percent control for thestandard fungicide (captan at 0.24% w. of formulated chemical). asfollows:

Foliage-fungicide activity index (F-F.A.I.)

1 percent control for treatment percent control for standard Where thedisease control for the test chemical and A further form in whieh thefungicidal compounds :of the present invention :may 'be'applied consistsof solutions of'the active ingredient in suitable inertliquid-orz'semisolid diluents, in which the active ingredients arepresent-in molecular ly dispersed form. l he form in which the agents tobe :employed :are applied tto the objects treateddepends on the :nature:oftheobjecfland thepurpose of the application.

Suitable inert solvents 'for the manufacture of liquid preparationsshould be inflammable, .as odorless as possible and without anytoxic-efiecton humans and animals when properly used. 'Neithershouldthey :have a corrosive etiect on the components of the preparations orT'ABLE 2.--FLIAGE FU'NGICIDE Tesr Foliage-fungicide activity indexActivitylndex at 0.24% Cone. (Upper figure) and %control 300.06% (LowerFigure) Phytoboxicity at 0.24% (upper figure) and 0.06% cone. (lowerfigure) respectively Chemical Compound Com- Com- 'P.i.* Sri. -E;p. U.a.C 1 bined T b C B On bined Index N- (1 ,4,5,6,7,7- Hexachlorobicyelo(2.2.1)hept-5-en 115 I06 100 129 133 115 200 75 2-yl-rnethyl)malein1ide100 100 100 100 I 100' '100 100 0 2- Chloro N- (1,4,5,6,7,7-hexachlorobieyclo (2.2.1) .100 125 95 11-8 250 75hept-5-en2-ylmothyDmalelmide "100 :89 89 -100 200 0 B P.i.=Ph1 t0phthorainfesta'ns (late blight oftomato).

S.a. =Septoria apii-graveolentic (late blight of celery). E.p.= Erysiphepol 1011i (bean powdery mildew). U.a,= Ur0m1/ces appendiculatus (beanrust). 0.1. Calletotrichmn lagemriu'm (cucumber anthracnose). bT=tomato, C=celery, B=bean, Cu=cneumber.

The active compounds of the present invention may be eused alone or incombination with other fungicidal, viricidal, insecticidal, oracaricidal materials, the action on which "may be either internal orexternal, with plant nutritives, .plant hormones and the like. Wettingagents, .and if necessary or desirable, stickers such as the heavyhydrocarbons oils with a minimum viscosity of Engler at 50 C. can bepresent. Any conventional wetting agent which will not react withthe'toxicant for example alkyl sulfate salts, alkyl Sary'l sulfonatesalts, su'lfosuccinate salts, .ethers of polyethylene glycols andalkylated phenols, and the like can be employed. If the toxic agents areemployed in the form of emulsions or suspensions, for example, in water,solvents such .as oils, emulsifiers, emulsion stabilizers and the likemay be added. Materials which suppress phytotoxic action may also beadded if desired. For example, glucose is known to protect tomato plantsagainst damage by certain substances having a phytotoxic effect whenemployed in concentrated form.

The 'irnides and maleimides of the present invention may be applied bymeans of spraying. .Spraying .of the plants to be treated may beperformed with aqueous emulsions solutions or suspensions of the activeagents. The spray .liquid is generally applied at a rate of from about75 to 150 gallons per acre. If spraying is effected with smallerquantities ofliquid as in low volume spraying, high concentrations ofthe active agents should be employed. If desired, a minoramount of theorder of about 0.01 to about 0.05% by weight, of a wetting agent may beadded to aid :in forming a suspension of the salt in the aqueous medium.Any of the conventional wetting agents 'can be employed. Particularlysuitable wetting agents are the sodium salts of a mixture of secondaryhep'tadecyl sulfates, sold commercially under the name of Teepol andpolyethylene glycol ethers of alkyl phenols sold under the trade name ofTriton X400 and Triton X-l55. Preferable concentrate compositionscomprising an active compound of the present invention and a .suitable.Wetting agent are prepared, :and the concentrate is then dispersed inwater prior to :use.

*the material of the storage vessel.

Examples of suitable solvents are high boiling oils, e.g. oils ofvegetable origin such as castor oil, etc, and lower-boiling solventswith a flash point of at least 30 C., such as carbon tetrachloride,ethylene dichloride, hydrated naphthalene, alkylated naphthalene,sorbent naphtha, etc. Mixtures of solvents may also be used.

The active compounds of the present invention may also be applied in theform'o'f dusts utilizing as the inert vehicle such materials astricalcium phosphate, precipitated chalk, bentonite, kieselguhr, etc.

These compounds may also be employed in the form of aerosols. For thispurpose, the active ingredient is dissolved or dispersed in a solventboiling below room temperature at atmospheric pressure.

We claim as our invention:

1. A polyhalo compound of the formula wherein X is a member of the groupconsisting of hydrogen and halogen, and at least one X is halogen, X isa member of the group consisting of hydrogen, halogen and lower alkoxy,R is selected from the group consisting of alkylene, phenylalkylene,tolylalkylene, naphthalenylalkylene and anthracenylalkylene in whichalkylene is in each case alkylene of 1 to 10 carbon atoms, and tolylene,phenylene, naphthylene and anthrylene, y is a whole number from 0 to l,and W is -a member selected from the group consisting of alkylene of 2to 5 carbon atoms, alkyleneof 2 to 5 carbon atoms, halosubstitutedalkylene of 2 to .5 carbon atoms, .halo-subsitutedalkenyleneof 2 to 5carbon atoms and .1 ,Z phenyI- ene, :andn is a whole number from 0 to 1.

2. A compound of the formula wherein W is straight-chain,halo-substituted alkylene 10 of 2 to 5 carbon atoms.

3. A compound of the formula CHrN XI X! K O wherein X and X are eachhalogen.

5. A compound of the formula wherein X and X are each halogen.

6. N-( 1,4,5 ,6,7,7-hexachlorobicyc1o(2.2. 1 )hept-S -en2-yl-rnethyl)maleimide.

7. 2-chloro-n (1,4,5,6,7,7 hexachlorobicyc1o(2.2.1)hept-5-en-2-yLmethyl)maleimide.

8. N (5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8aoctahydro -1,4,5,7-dimethanonaphthalen -2- y1methyl)- maleimide.

9. 2,3 dichloro -N- (1,4,5,6,7,7 hexachlorobicyclo- (2.2.1-hept-5-en-2-y1methyl) succinimide.

10. N-( 1,4,5,6,7,7-hexachlorobicyc1o(2.2. 1 )hept-S-en- Z-yl)-ma1eimide.

11. The method of combatting fungi on living plants comprising applyinga fungicidal toxic amount of N- (1,4,5,6,7,7hexach1orobicyc1o(2.2.1)hept 5 en 2- ylmethyl)maleimide to said plants.

References Cited in the file of this patent UNITED STATES PATENTS2,015,045 Teichmann Sept. 17, 1935 2,593,840 Buc Apr. 22, 1952 2,638,431Harry May 12, 1953 2,642,373 Dazzi June 16, 1953 2,698,850 Long Jan. 4,1955 2,795,589 Bluestone June 11, 1957 2,813,877 Lambrech Nov. 19, 1957

1. A POLYHALO COMPOUND OF THE FORMULA
 4. A COMPOUND OF THE FORMULA